TW201105728A - Polymeric articles comprising oxygen permeability enhancing particles - Google Patents

Abstract

The present invention relates to a composition comprising a hydrogel polymer having less than 100%haze, and distributed therein an oxygen enhancing effective amount of oxygen permeable particles having an oxygen permeability of at least about 100 barrer, average particle size less than about 5000 nm.

Description

201105728 VI. INSTRUCTIONS: RELATED APPLICATIONS This patent application claims to be based on U.S. Patent Application Serial No. 12/721,081, filed on March 10, 2010, filed on March 31, 2009. U.S. Provisional Patent Application No. 61/164,931; and U.S. Provisional Patent Application Serial No. 61/252,279, filed on Oct. 16, 2009. TECHNICAL FIELD OF THE INVENTION The present invention relates to a polymer member comprising oxygen permeable reinforcing particles and a method of forming the same. [Prior Art] In many applications, a polymer material having oxygen permeability is required. These applications include medical devices. Contact lenses are one of them. Gas permeable soft contact lenses are made of conventional hydrogels and australis resin hydrogels. Conventional hydrogels consist mainly of hydrophilic monomers, such as 2-hydroxyethyl methacrylate (HEMA), N-vinyl 咐 咯 咯 (N_viny丨pyrr〇lid〇ne, Nvp Prepared with a monomer mixture of vinyl alcohol. The oxygen permeability of these conventional hydrogel materials is related to the water content of the material, typically less than about 20 to 30 barrers. For contact lenses made from traditional hydrogel materials, the degree of oxygen permeability is suitable for short-term wear; however, in the case of long-term wear of contact lenses, such a degree of oxygen permeability may not be sufficient to maintain the cornea. Health (for example, no removal for 30 days). 201105728 Silicone resin hydrogel (siH, s) is also used in GPSCL. The epoxy resin hydrogel is typically prepared by polymerizing a mixture comprising at least one neodymium-containing resin monomer or reactive macromonomer, and at least one hydrophilic monomer. While such lens materials can reduce corneal edema and high vascular distribution associated with conventional hydrogel lenses, the indole resin component is incompatible with hydrophilic components, making such materials difficult to manufacture. In the case of the need to extend the collocation, the material is more improved and has a demand for protein absorption characteristics, wettability and general eye comfort. Polyoxyphthalate elastomer contact lenses have also been used. Although this piece has a good transparency, its secret and mechanical properties are very poor. Strengthening Shixi fiber has been exposed to enhance the elastic properties of the dream oxygen resin. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition comprising a polymer of oxygen-effective amount of oxygen-permeable particle distribution = at least Γ, having an average particle size of less than about 5 〇〇〇 nm. The secret is the implementation method] The "medical device" used in this article is ==; or the object used by r. These devices are: 曰·曰& implants, drainage strips and ophthalmic devices such as 1 device gossip contact lenses, preferably invisible eyes made of hydrogels 4 201105728 As used herein, "lens" refers to Ophthalmic device stored in it. These devices can provide optical 妒 艮 艮 艮 月 疋 疋 疋 疋 疋 疋 疋 疋 疋 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Product, diagnostic assessment or ageing, or any combination thereof. (10) here includes but is secretive of soft contact lenses, hard contact lenses, artificial waters 3 and „ , , , , , , , , lenses , ocular inserts and optical inserts. "Milk mixture" means a mixture of ingredients, including the reaction components, diluents (if used), initiators, cross-linking-additives, depending on the polymer formation conditions in the formation of the polymer. The reactive component refers to the component of the reaction mixture which, when polymerized, becomes a permanent part of the polymer via chemical bonding with the polymer matrix or by embedding or entanglement. For example, the reactive monomer becomes part of the polymer via polymerization, and the non-reactive polymeric internal wetting agent, such as PVP and the oxygen permeable particles of the present invention, is physically embedded as part of the polymer. The diluent (if used) and any additional processing aids, such as deblocking agents, do not become part of the polymer and are not part of the reaction. The reaction mixture of the present invention can be formed by any method known in the art to form a polymer or device, including agitation, rolling, kneading and shaking, "biocompatibility" and "bioaccumulation". """ means that the material in question does not cause any significant adverse reaction when in contact with the desired biological system. For example, when the contact lens contains oxygen permeable particles, the adverse reactions include stinging, inflammation, poor levels of protein and lipid uptake, ocular cell damage and other immune responses. 201105728 "Hydrogel" polymer means a polymer that absorbs or absorbs at least about 20% by weight of water, in some embodiments at least about 30% by weight of water, in other embodiments. At least about 40% by weight of moisture. The oxygen permeable particles have an oxygen permeability of at least about 100 barrer, in some embodiments from about 100 to about 100 barrer, and in other embodiments from about 300 to about 1 barrer. . Oxygen permeable particles can also have an oxygen permeability of at least about 300, 400 or 500 barrers. The oxygen permeable particles of the present invention may be solid or filled or hollow particles. The solid oxygen permeable particles may be formed by crosslinking a polymer such as a fluoropolymer, a cross-linked polydialkylsiloxane polymer, a self-assembled decane and a rigid material such as poly A crosslinked polymer of polytrimethylsilylpropyne and combinations thereof. In one embodiment, the oxygen permeable particles are non-reactive, which means that in the case of using the composition of the present invention, the oxygen permeable particles are not covalently bonded to the polymer, but may be by dipole-even Dipole-dipole forces such as hydrogen bonds or der Waals forces are combined with the polymer. If the oxygen permeable particles are encapsulated, the oxygen permeable particles are not covalently bonded to the encapsulating material, and the encapsulating material is not bonded to the oxygen permeable particles or the polymer. . In one embodiment, the surface of the oxygen permeable particles is reactive to assist in the diffusion and/or stabilization of the oxygen permeable particles in the selected reaction mixture. 6 201105728 'An anion or a cation means that the molecule has potential ionicity. An example of a potential rider's official test is - lining, an example of a latent anionic g-energy group is - amines, especially - tertiary amines. The oxygen permeable particles selected by this method do not significantly reduce the optical properties of the polymer, including color and sharpness. This object can be achieved by controlling the particle size, refractive index or chemical properties of the oxygen permeable particles or any combination thereof. The oxygen permeable particle has a refractive index within about 20% of the refractive index of the aqueous polymerization mixture. In some embodiments, it is within about 1 G% of the refractive index of the aqueous polymerization mixture. Other embodiments may use oxygen permeable particles having a refractive index of about 1% of the refractive index of the aqueous polymeric compound, and in other embodiments less than 〇·5%. In the embodiment, the oxygen permeable particle is in a particle size; the enthalpy is between about 2Q〇 and i〇Q〇 nm, and the refractive index is within about 1% of the refractive index of the aqueous polymerization mixture. Oxygen permeable particles having a particle size of less than 200 nm may have a refractive index within about 20% of the aqueous polymer mixture. In one embodiment, the polymer refers to a hydrogel suitable for the preparation of contact lenses having a refractive index between about 1.37 and about 1.45. In one embodiment, the hydrogel polymer has a refractive index between about 1.39 and about 1.43, and the encapsulated oxygen permeable particles have a refractive index within the above range. In one embodiment, the osmotic particles are included in the ophthalmic device, and in another embodiment the osmotic particles are at least one location outside the optical zone of the contact lens. This optical zone refers to the focus of the light. Larger particles having a mismatched refractive index can be tolerated in this embodiment. Therefore, the average particle size of the contact lenses prepared according to this embodiment may be between about 2 〇〇 nm and 1 〇〇 nm. 201105728 Solid oxygen permeable particle solid oxygen permeable particles may be formed from a material including a sulphur oxide resin, a crosslinked polymer of fluorine, and a combination thereof, or a material and the like of an oxygen permeable perovskite oxide and a combination thereof. . Specific examples of the polymer containing a decyloxy resin include polydimethyl siloxane (PDMS), cross-linked poly(dimercapto methoxy), poly((trimethyl decyl)propyne), and a parent t (dimethyl oxalate) core and a polydioxyl sulphate / with t (half sesame oxygen) (p〇ly (silseSqUi〇xane), DMS / POSS) core / shell, shell can Obtained by Shin Etsu, Inc. (Japan) under the name X-52-7030, having a size ranging from 0 2 to 2 〇〇〇 nm and an average particle size distribution of 800 nm. Examples of fluoropolymers include amorphous fluoropolymers such as 2,2-bis(trifluoromethyl)-4,5-difluoro-indole, dicarbazole and tetrafluoroethylene (trade name TEFLON) AF sold) copolymers, fluorinated polydidecyl alkane and fluorinated polynorbomene. Copolymers and mixtures containing the foregoing materials may also be used as long as the oxygen permeable particles have the oxygen permeability range disclosed herein. In one embodiment, the solid oxygen permeable particles comprise at least one inorganic material, such as a metalloid such as boron nitride, a metal oxide, including iron oxide, oxidized, titanium oxide, oxidized, metal, such as gold, transition metal. Sulfides' such as ZnS and CdS' graphite flakes, inorganic/organic hybrids such as full shell coated with metal oxides of cellulose. It is also possible to use a copolymer containing the foregoing and a mixture comprising any of the foregoing and inorganic materials. Suitable solid oxygen permeable particles have an average particle size of less than 5000 nm, in some embodiments less than about 1000 mn, in some embodiments 8 201105728 less than about 800 ηιη, in some embodiments less than about 600 nm, in others In the examples, hollow nanoparticles having a size of less than about 200 nm are otherwise selected such that the oxygen permeable particles are hollow. A suitable hollow nanostructure has a watertight hard shell that encloses or encloses an inflatable space. Hollow nanostructures are permeable to gases such as oxygen and air, and have an oxygen permeability of at least about 200 barrer for oxygen. In a """* some examples are at least about 300 barrer, In some embodiments, it is at least about 500 barrer, and in other embodiments, greater than about 1 Torr barrer. The hollow nanostructures of the present invention have different names, including nanostructures, nanospheres, microcapsules, balloons, and microspheres. The above known nanostructures can be used as long as they have the characteristics described herein. Suitable hollow nanostructures include synthetic hollow nanostructures and balloons. The balloon (or balloon protein) can be naturally found in bacteria, with a protein shell enclosing an inflatable space. The synthetic nanostructures comprise an outer shell formed from a polymer, a metal oxide, a metalloid, carbon, and combinations thereof. When the oxygen permeable particles are in a hollow nanostructure, the hollow nanostructure has a particle size 'in the longest dimension, less than 500 nm, in some embodiments less than about 400 ηιη, and in other embodiments only about 10 About 100 nm. In one embodiment, the hollow nanostructure has an average diameter of from about 2 到 to about 100 nm and a length of from about 5 〇〇 nm. The nanostructure may have any closed, hollow structure, including a closed-end cylindrical, spherical, oval, regular or irregular polyhedron, ellipsoid, cone, ellipsoid (which may be described by its 3 major axis length). Structure or irregular shape. Naturally occurring nanostructures such as the gas 201105728 capsule, usually a cylinder with a tapered end. The synthetic nanostructure may be of any shape, and in the embodiment, it may be cylindrical and spherical. The hollow nanostructured outer shell is permeable to gases, particularly oxygen, to mixtures containing oxygen, such as air. Gases such as oxygen and air are free to penetrate the hollow nanostructure of the present invention. The nanostructured outer shell of the present invention has an oxygen permeability of up to about 5 barrers, and in some embodiments at least about 20 barrers. In one embodiment, the outer casing has an oxygen permeability equal to or greater than the oxygen permeability of the matrix polymer. However, compared to the nanostructure, since the thickness of the outer shell is relatively thin (less than about 10 ηηι, in some embodiments, between about 1 and about 5 nm), the outer shell material having a relatively low oxygen permeability still has its usefulness. Since the gas can diffuse freely through the hollow nanostructure, the liquid does not (especially water) the nanostructure retains its shape by the rigidity of its outer shell material. The outer shell material has a modulus of at least about 1 GPa, in some embodiments at least about 2 GPa, and in some embodiments, from about 2.5 GPa to about 3.5 GPa. It is known that a stable shape can be maintained under pressure, including the shape of a sphere and a cylinder, a cone and an ellipsoid (which can be described by its three major axis lengths), and combinations thereof. In one embodiment, the hollow nanostructure is constructed as a sphere. In other embodiments, the sphere has an average diameter of about 2 〇〇 mn. The δ metastructure may also include reinforcing structures such as ribs, reinforcing fillers, nanofibers, structural proteins, cross-linking (ionic or covalent) combinations of their structures, and the like. The hollow nanostructure of the present invention maintains its hollow structure without collapse when it is prepared, extinguished, and incorporated into an object. The retention or retention of the hollow nanostructure is characterized by a critical pressure of 10 201105728 of at least about 〇 5 MPa, in some embodiments from about 0.1 MPa to about 0.3 MPa, and in other embodiments greater than 0.2 MPa. The protein of the outer layer of the nanostructure is generally hydrophilic, and the inner layer of the protein is impervious. This property allows the nanostructure to be dispersed in a hydrophilic substrate polymer, such as a hydrogel, and to prevent moisture from penetrating into the inflatable cavity. The inner and outer layers of the nanostructured outer shell may be formed by layering, such as polymer delamination, protein or other outer shell material, or from a hydrophilic portion facing outward, the hydrophobic portion toward the hollow nanostructure interior, or toward the shell An amphiphilic material of the hydrophobic layer within the layer is formed. The hydrophilicity and water permeability characteristics of the material suitable for forming the nanostructure can be defined by the water permeability coefficient at 25 ° C and the surface tension. A hydrophilic material suitable as the outer layer structure of the outer shell has a water permeability coefficient of greater than about 1 Torr and a surface tension of greater than about 40 dyne/cm at 2 °C. A water-impermeable material suitable as the inner layer structure of the outer casing has a water permeability coefficient of less than about 1 Torr at 25 ° C and is 2 Å. Under the armpit, the surface tension is less than about 35 dyne/cm. In some embodiments, the hydrophilic material exhibits a junction angle of less than about 8 〇 when measured at room temperature using Wilhelmy plate meth〇d and distilled and deionized water. The water impermeable material exhibits greater than about 1 Torr. The junction angle. In the Polymer Handbook (p〇lymer Handb〇〇k), 4th edition, edited by J. Brandrup, lmmergut, Ε Ή, Grulke, e A,

Bloch, D, has reported the permeability coefficient of many polymers. In an embodiment, the hollow nanomaterial is synthesized. Examples of suitable synthetic methods include physicochemical methods in which the outer shell material is formed during the evaporation of the solvent or in a controlled electrostatic or chemical interaction. An example of this method is disclosed in the Nature of January 20, 1994, 201105728 _ (Nature), Volume 367. The hollow nanomaterial may be formed by phase separation in which a solvent containing a polymerization mixture of two or more polymers is evaporated. The choice of surface tension and evaporation rate is based on the dispersion balance of the two liquids such that the spherical droplets of one polymer are covered by a uniform layer of another polymer, forming an emulsified droplet suspension in the solvent. When a different material is used as the inside and outside of the nanostructured outer casing, the material formed by the outer hydrophilic layer may be a crosslinked or self-polymerized polymer. Examples of such materials include 2-hydroethyl methacrylate ((ΗΕΜΑ)), poly vinyl acetate, methacrylic acid, N-ethylene sulphate N-vinylpyrrolidone, N-vinyl acetamide, N-vinyl methyl acetamide, N, N-dimercapto propylene Indoleamine, acrylic acid, glycerol monomethacrylate, 2-methacryloxyethyl phosphorylcholine (MPC), methyl methacrylate Methyl methacrylate ), hydroxyethyl acrylate, N-(l,l-dimethyl-3-oxybutyl)acrylamide (N-(l,l-dimethyl-3-oxybutyl) acrylamide ), polyethylene glycol monomethacrylate, polyethylene glycol dimethacrylate, 2-ethoxyethyl methacrylate 2-mercaptopropene oxyethyl choline (2-methacryloxy) Ethyl phosphorylcholine) and combinations and analogs thereof. Other polymers having the above water permeability coefficient and surface tension can also be used. Examples include polysaccharides, hydrophilic polypeptides, 201105728 polyacetate, polyamines, nylons including carbon repeats having at least 4 carbon atoms, polyamines, protein vinegar, cellulose, and having hydrophilic branches A combination of a hydrophobic backbone polymer and a combination thereof that provide the above-described water permeability coefficient and surface tension. Specific examples of the polymer which can form the outer layer of the outer shell include poly(acrylamide co-acrylic acid), poly(N-isopropylpropionamide) (poly(N-) Isopropylacrylamide)), 2-hydroxy methacrylate includes polymers and copolymers, polyvinyl alcohol polymers and copolymers and the like. The polymer can have any shape including linear, branched and brush-shaped structures. In one embodiment, the outer layer of the outer shell is a crosslinked polymer formed from at least one monomer forming the matrix. Examples of materials which can form the inner layer include homopolymers and copolymers, including polyorganosiloxanes (including silicone methacrylates), fluoropolymers, liposomes (liposomes). ), hydrophobic polypeptides, polyesters, 1醮fee (polyamides), poly(s), polystyrenes, polyaniline, polypyrroles, and Combinations and analogs. Examples of suitable inorganic materials include oxygen-permeable perovskite oxides, metalloids such as boron nitride, metal oxides including iron oxide, aluminum oxide, titanium dioxide, oxidization, metals such as gold, transition metal sulfides For example, ZnS and CdS, graphite flakes, inorganic/organic mixtures such as full-shell coated cellulose metal oxides and polytetrafkioroethanes, and combinations and analogs thereof. Specific examples of the polymer containing the diabase resin include polydimethyl siloxane oxime 201105728 (polydimethyl siloxane, PDMS), poly(dimethyl siloxane), poly (dimethyl sulfonate) Oxygen burn (poly(silsesquioxane)) or poly((trimethy 1 silyl) propyne). Specific examples of the fluoropolymer include amorphous fluoropolymers (e.g., 2,2-bis(trifluoromethyl)-4,5-difluoro-1,3-di[oral + oxime] oxazole ( 2,2-bis(trifluoromethyl)_4,5-difluoro_l,3-dioxole) copolymer with tetrafluoroethylene (sold under the trade name TEFLON AF), fluorinated fluorinated polydimethyl fluorene oxide With fluorinated polynorbornene (polynorbornene). Mixtures containing the foregoing copolymers and any of the foregoing inorganic materials may also be used. The inner layer material may include a latent reaction group such as pentafluoromethacrylate and N-acryloxysuccinimide ° US 2004/0120982 to disclose suitable latent reaction groups, which may It is added to the inner layer of the outer casing to allow the reaction to take place between the inner and outer layers of material. In other embodiments, the outer layer of the outer casing and the outer layer of material have alternating charges to allow the material to be bonded by charge interaction. Examples of such materials include carboxylic acid metal salts, carb xylic acid/quaternary ammonium salts, suif〇nic acid metal salts, and acid / suifonic acids/quaternary ammonium salts. Alternatively, the outer casing may be formed from one or more zwitterionic materials, amphoteric materials, or combinations thereof. Suitable zwitterionic and microcellular materials are as follows. The combination of the amphoteric materials is such that the hydrophobic portion is inwardly directed toward the nanostructure to form a cavity' and the hydrophilic portion is directed outwardly toward the substrate. The amphoteric material is then crosslinked in 201105728 to form a nanostructure of the desired size, shape and modulus. In another embodiment, the hollow nanostructure can be formed around a daughter or template particle' which is removed after formation of at least a portion of the nanostructure. In the present embodiment, a polymerization reaction such as emulsion polymerization, microemulsification polymerization, suspension polymerization or formation of liposomes or micelles followed by crosslinking can be used to form an outer shell layer. Suitable templating materials include polymeric microspheres, water-in-oil emulsified droplets, liquid-directed liquid crystals having a polylayered vesicular structure. A suitable seed or template can be removed by calcination or solvent etching after the outer shell or shell has been formed. An example of such a synthetic method is "Graphene: A Perfect Nanoballoon,,, Leenaerts et al., Applied Physics Letters, 93, 193107 (2008). Dept Physics, Univ. Antwerpen; "Growing Nanoballoons and Nanotubes of Pure polymer from a Microcapsule" , Fei et al., Inst. Textiles, Macromol. Rapid Commun. 29 1882-1886, (2008). The Hong Kong Polytechnic University ; "Silicone Nanocapsules Templated Inside the Membranes of Cationic Vesicles", Kepczynski et al., Langmuir, 23 7314-7320, (2007). Jagiellonian Univ·Krakow Poland; “Encapsulation of Inorganic Particles with Nanostructured Cellulose”, Nelson and Deng, Macromol. Mater. Eng., 292 1158-1163, (2007). Georgia Tech. ; “Stable Polymeric Nanoballoons: Lyphilization and Rehydration of Cross-linked Liposomes", Liu and O'Brian, J. Am. Chemical Society, 124 6037-6042, (2002), Chemistry Dept. Univ. Arizona ; 201105728 ''Nanoparticles and nanoballoons of amorphous Boron coated with crystalline boron nitride", Appl. Phys Lett. 79, 188 (2001); "Carbon Nanoballoon Produced by Thermal Treatment of Arc Soot", New Diamond and Frontier Carbon Technology, 15 No 2 (2005). Toyohashi University of Technology Japan ; Fabrication of Core-Shell Fe3 O 4 /polypyrole and Hollow Polypyrole Microspheres, Polymer Composites 2009. Lu et al" in Jilin University, China. These disclosures are hereby incorporated by reference. Other options for carbon hollow nanostructures can be removed via arc soot treatment above 2400 °C. Macromol. Mat. Eng. 2007 292, 1158-1163 "Encapsulation of Inorganic Particles with Nanostructured Cellulose". In another embodiment, the nanostructure can be self-bacterial, such as from cyanobacteria (like Naturally-generated airbags are isolated from Anabaena, Microcystis, Ocillatoria, and methogens and salt-producing organisms. Naturally generated balloons can be borrowed from WO 98. The conventional method disclosed in /21311 is hereby incorporated by reference. The isolated naturally occurring nanostructures can be "as-isolated" or coated as disclosed herein or Used in an encapsulated manner. 201105728 The oxygen permeable particles (both solid and hollow) can be encapsulated in the reaction mixture before they are prepared. This method is at the core of the solid oxygen permeable particles or 仏The nanostructure is particularly useful when it is prepared from a water-impermeable material or an amphoteric material. The "encapsulation" herein refers to embedding the oxygen-permeable particles around the oxygen-permeable particles or other materials by other materials. . The encapsulation means comprises coating the oxygen permeable particles, entrapping the oxygen permeable compound with other materials to form, for example, liposomes, micelles, polymeric structures surrounding the oxygen permeable particles, Combinations of the same are similar. The oxygen permeable particles may be encapsulated for a number of reasons. For example, when embedded in a medical device, the oxygen permeable particles may be coated with a polymer to avoid an immune response. In one embodiment, the oxygen permeable particles may be encapsulated to modify particle characteristics, for example, to make them more compatible with the components of the reaction mixture used to prepare the compound. In one embodiment, the particles may Encapsulated to help maintain a desired particle size, to avoid or limit aggregation, or to provide other desirable characteristics of the final article, such as, but not limited to, refractive index, biocompatibility (including immune response, protein or lipid uptake), combinations thereof And similar. For example, the oxygen permeable particles may be encapsulated in a hydrophilic outer shell and dispersed in the reaction mixture, in addition to exhibiting an enhanced reaction with the hydrophilic reaction mixture. Capacitance, encapsulation also avoids the formation of a hydrophobic side in the lens formed by the reaction mixture. The hydrophobic side may cause denaturation of the protein or stain the mirror. Other reasons for encapsulation and its benefits are common in the art to which the present invention pertains. It is well known to the skilled person. In one embodiment, the oxygen permeable particles may be dispersed or suspended in the reaction mixture. The particles may be dispersed by ionic or steric barrier force 201105728 (steric force) or a combination thereof. In one embodiment, the oxygen permeable particles form a stable dispersion comprising particles having a size of less than about 1 〇〇〇 mn, which can remain dispersed for at least about one hour, in some embodiments at least about one day 'in some embodiments. For a week or more. In one embodiment, the reaction mixture may further comprise at least one surfactant. Suitable interfacial agents are compatible with the reaction mixture and the suspended or dispersed particles and do not cause haze. Suitable interfacial agents include small molecule interfacing agents, polymeric surfactants, amphoteric copolymers, combinations and similarities thereof. Examples of suitable interfacial agents include PEG-120 mercaptoglucose dioleate (DOE 120, available from Lubrizol), PVP, poly vinyl alcohol/polyvinyl acetate (p〇ly vinyi acetate) copolymer , amphoteric statistical copolymer or block copolymers 'such as oxime resin / PVP copolymer, polyalkylmethacrylate / hydrophilic copolymer, organic oxalate compound (organoalkoxysilanes), for example, 3-aminopropyltriethoxysilane (APS), methyl-triethoxysilane (MTS), phenyl-triethoxylate Phenyl-trimethoxysilane (PTS), vinyl triethoxysilane (VTS), 3-glycidoxypropyltrimethoxysilane (GPS), having a molecular weight greater than about 10,000 And comprising a silicone resin macromolecule, such as a hydrogen bond group, such as, but not limited to, a thiol group and a mixture thereof. An interface composed of a surfactant. 201105728 When the dispersant is a polymer, its molecular weight has a range. A molecular weight of about 1,000 to several millions is possible. The upper limit is limited only to the solubility of the dispersant in the reaction mixture. When a dispersant is used, the dispersing amount is from about 〇1〇 to about 40% by weight of all components in the reaction mixture. In some embodiments, the dispersing amount is from about 0.01% to about 3% by weight, and in other embodiments, from about 0.1% to about 30% by weight. In some embodiments, the dispersing agent is also a reactive component that forms a polymeric member, such as when a contact lens comprising polyvinyl alcohol is formed. In these embodiments, the dispersing amount used can be up to about 90% by weight, and in some embodiments up to about 100% by weight, based on the weight of all ingredients in the reaction mixture. In one embodiment, the oxygen permeable particles are coated with a coating composition. A suitable coating composition can be selected to provide any of the above characteristics. For example, when it is desired to have compatibility with a conventional hydrogel reaction mixture, suitable coating compositions include anions, latent anions, cations, latent cations, zwitterions, non-polar coating compositions, combinations thereof and the like. . Examples of anionic and latent anionic polymers which can be used as coating materials include polyacrylic acid, hyaluronic acid, dextran sulfate alginates, copolymers or combinations thereof or the like. Examples of cationic and latent cationic polymers include poly(diallyldimethylammonium chloride) (PDADMAC) polytosine (chitosan), poly(quaternary gas compound) (poly(quats)) ), polyamines, polypyridyls, copolymers or combinations or analogs thereof. 19 201105728 Examples of zwitterionic polymers include poly (sulfobetaine) and poly (carboxybetaine) , poly (phosphobetaine), copolymer or a combination or analog thereof. Examples of zwitterionic polymers include (poly(3-[ΛΜ:2-propenylaminoethyl)dimethylammonium] Propane sulfonate), poly(3-|W-(2-methacrylamidoethyl)di-F-ammonio]propane sulfonate), poly(3-[Λ42-methacrylic acid) dimethyl Ammonium]propane sulfonate, polydimethylethylene-phenyl)-enyl)propanone, poly(3-[ν·(2-propylamidocarboxylate) dimethyl) Recording base] propionic acid), poly(3_[w_(2_mercaptopropenylamino)dinonyl ammonium]propionate), poly(3_[#_(2_methacrylamidoethyl) Dimethylammonium]propionic acid, (3-(;V,AL-diylethylene-phenyl)-ammonio)propionate and poly(2-mercaptopropenyloxyethylphosphocholine). In some embodiments, The anionic and zwitterionic or cationic and zwitterionic coating compositions comprise an outermost layer. The oxygen permeable particles can be coated with one or more layers. Suitable coating methods include 1) anionic/cationic polymers, polyacids/poly Alkaline or polymeric hydrogen donor/hydrogen species alternate layer deposition, 2) electropolymerization '3) via traditional or controlled entrapment and dispersion grafting (co)polymerization, 4) to small; = early chemical modification 'eg grafting, or 5) chemically determined == ie acid/catalyzed hydrolysis, ray, gamma ray or:: 羼: surface modification of the lamp particles. Other Modifications Polymerization and controlled gas plasma deposition. The oxygen permeable particles are encapsulated in the micelles. It can be formed by reading (four), including a shirt/dissolved polydimethylinner liquid to form a water-in-oil (oiMn-water) emulsion or microemulsion with a suitable medium 201105728, 2) forming an emulsion/microemulsion, An active oxygen generating resin is then formed, wherein the reactive epoxy resin may be composed of an oligopolymer including, but not limited to, a decyl alcohol functional polydialkylsiloxane, 3) forming an emulsion/microemulsion, followed by formation An active diabase resin, wherein the reaction oxime oxy-resin may comprise, but is not limited to, a vinyl- or allyl-functional polydialkyl siloxane with a hydride functional group The oligomeric polymer mixture of polydialkyl siloxane consists of '4) using an ethylene oxide alkoxy macromonomer such as, but not limited to, a polydialkyl alkane, such as mPDMS (monodecyl propylene oxypropylene) Mono-n-butyl terminated polydimethylsiloxane ' OHmPDMS (mono(3-mercaptopropenyloxy-2-hydroxyloxy)propyl terminated mono-butyr Polydimethyl oxime Mono-butyl terminated polydimethylsiloxane, mono-butyl terminated polydimethylsiloxane The macromonomer of the ester (Methyl-bis(trimethylsilyl〇Xy)_siiyi_pr〇pyigiyCer〇i_dim ethacrylate)) or a combination thereof is prepared by emulsion/microemulsion radical polymerization to prepare a decyloxy-containing latex. The above decyloxy-emulsification/microemulsification can also be prepared directly in a monomer reaction mixture with appropriately selected monomers and diluents. The particles formed by the above emulsification/microemulsification can be further stabilized by introducing a crosslinking agent during the hardening process. The choice of the crosslinking agent is based on the function of the reactive oxirane resin used in forming the particles. Examples of the conventional oxirane cross-linking agent include: 201105728 is not limited to SiMAA DM (methyl bis(trimethyl sulphate)-stone propyl glycerol dimercapto acrylate g), and four smoldering smoldering ( Tetra-alkoxy silanes), polyvinyl esters, propylene esters, silyl-hydride moieties and hydrosilylating moieties with suitable metal catalysts. The decyloxy-emulsification/microemulsification can be formed from a number of surfactant systems, including ionic and nonionic detergents. The surfactants commonly used in the preparation of latexes can be used, as is well known to those of ordinary skill in the art. Examples of such surfactants include, but are not limited to, alkyl sulfates, alkyl sulfonates, alkyl benzene sulfonates, fatty acids, alkyl polyoxyethylene ethers, geminyl salt, and alkyl glucocides. ), a polysorbate or a combination of surfactants. In the preparation of a silicone resin microemulsion system, a reactive surfactant can also be used. Also known in the literature as "surfmers", these interface-active compounds contain a reactive functional group at the hydrophilic or hydrophobic end and are capable of participating in the polymerization process, thereby incorporating themselves into the final polymeric particles, thus eliminating the need to move In addition to the surfactant, or to minimize the need to remove. Materials that can be used to form the oxime resin microemulsified particles include, but are not limited to, allyl polyalkylene glycol ethers, vinyl polyalkylene glycol ethers, Allyl polyalkylene glycol ether sulfates, alkyl methacrylates and vinyl polyethylene glycol ethers ). These vehicles can be combined or combined with the above standard emulsion polymerization surfactants. 0 22 201105728 In addition to lower molecular weight surfactants, polymeric surfactants and emulsifiers can also be used to prepare decyloxy-emulsions/microemulsions. Examples of such polymeric surfactants are well known in the art to which the present invention pertains, including but not limited to polyether/poloxamer surfactants, N-vinylpyrrolidone (co)polymers, and many hydrophobics. A surfactant of a copolymer of a monomer and a vinyl alcohol, a poly(ethylene-co-maleic anhydride) or a combination thereof. Examples of the decyloxy-latex prepared by radical microemulsification polymerization include the use of a vinyl alkoxy macromonomer, for example,

Macromonomers including, but not limited to, SiMAA2 DM, OHmPDMS and/or mpDMS or combinations thereof, for the simple synthesis of high Dk (oxygenation coefficient) particles of the tunable composition, thus controlling structure and properties. In general, the present embodiment comprises a microemulsion comprising an above-mentioned surfactant or a combination of the above-mentioned surfactants, at least one decyloxy macromonomer, and a crosslinking reaction monomer in water ( For example, SiMAA2 DM, EGDMA (ethylene glycol oxime dimethacrylate) or DVB (divinylbenzene) and a water-soluble radical initiator. According to the choice of initiator, the polymerization It can be initiated via a thermal, photochemical or redox pathway. In a preferred embodiment, the ratio of OHmPDMS to SiMAA2 DM can be varied to obtain final particles with tailored physical properties including, but not limited to, desired refractive index coefficients. Values and increased particle stability. In the above examples, "water soluble free radical initiator" is defined as any compound that produces one or more activities under certain conditions (eg, temperature, light intensity, and wavelength). Base species. These compounds are known to those of ordinary skill in the art to which the present invention pertains. Free water solubility can be used in the examples. Examples of initiators include, but are not limited to, VA-(M4(2,2.-azobis[2-(2-dihydroimidazol-2-yl)propane] dihydrochloride), V-50 (2,2) '-Azobis(2-mercaptophenylpyrene) dihydrochloride), VA-057 (2,2'-azobis[N-(2-hydroxyethyl)-2-mercaptopropene] Hydrate), VA-060 (2,2,-azobis{2-[1-(2-hydroxyethyl)-2-dihydroimidazol-2-yl]propane; dihydrochloride), VA_ 〇61 (2,2,_azobis[2_(2-dihydroimidon-2-yl)propane]), VA_〇67 (2,21-azobis (1_imine)咬-·2_ethylpropane) dihydrochloride), VA-80 (2,2,-azobis{2-methyl-N-[l,l-bis(hydroxyindenyl)_2_hydroxyl) Base] propylamine 、, va_〇86 (2,2'-azobis|>methyl_N_(2_hydroxyethyl)propanamide]), νρΕ·〇2〇1 (poly(B) Glycol) giant initiator MW = 2000 g/mole), VPE-0401 (poly(ethylene glycol) giant initiator MW==4〇〇〇g/in〇ie), vPE-〇602 聚聚( Ethylene glycol) giant initiator Mw = 6〇〇〇g/m〇le), potassium persulfate, water, gluten-based photoinitiator. The invention is not limited to the use of water-soluble self-priming agent. Traditional oil soluble starter In an alternative embodiment, a water-soluble radical initiator: such as Z, ^, the final characteristics of the particles prepared by deuteration/microemulsion polymerization, the final ί rt using a hydroxy group - or The interface properties of the PEG functional starter taboo may be modified; and thus limited to increasing surface enthalpy, hydrophilicity, resulting in biocompatibility. The surfactant oxygen permeable polymer particles may be stable with or may be Λ: at a temperature of two, "°, possibly with a stable surfactant phase, I J is embedded in a stable surfactant. The particles may be negative 24 201105728 A core/shell structure containing a high Dk (oxygen permeability coefficient) material in the core with a stable surfactant and other stability in the outer shell. Once formed, the microcell may form a total with the hydrogel polymer. 4 shell bonds, may be combined with a hydrogel polymer, or may be physically embedded in a hydrogel polymer. The micelle may have a core/shell structure. Optional to form a suitable composition for cell coating To provide any of the above characteristics. For example, when compatible with a conventional hydrogel reaction mixture, suitable microcell compositions include the yield of the final particles, anionic, cationic zwitterionic or non-polar microcellular surfaces. The portion located on the surface of the microcell particles can be introduced during the emulsification/microemulsification process by using an epoxy resin-reactive covering agent or a surfactant. An anionic, cationic or zwitterionic polymer can be used to form the microcapsule coating as long as it is compatible with the cation, zwitterionic or anionic functional group disclosed herein and the other end is compatible with the oxygen permeable particle. Examples of the moiety at the hydrophobic end include alkoxydecane, polychlorinated decane, vinyl decane, polyfunctional propyl moiety (p〇lyfuncti〇nal allyl moieties), polyglycol-hydrogenate ( Polsilyl-hydrides), aliphatic linkers (usually propyl or butyl), etc. Monomers and oligomers can also be used to form micelle coatings in the present invention. Specific examples include by Wacker Metroark. The alkylbenzene sulfonate and the alkyl ethoxylate prepared by the method disclosed in IN 2003 K000640 of Chemicals Ltd. Other patents comprising the polymerization of the oxime resin ME include U.S. Patent No. 5,612, 215 and U.S. Patent No. 6,316,541. Suitable methods for microcapsule coating include the yield of the final particles, anionic, cationic, zwitterionic or non-polar microcapsule surface. This micro25 201105728 is a part of the cell surface that is emulsified. The towel can be introduced by the oxy-resin _reactive coating or the surfactant. The covering agent is also surface-active and contains at the end-hydrophobic resin _ reactive part (including but not limited to Anthracite, polyoxane, vinyl decane, polyfunctional allyl moiety and polyfluorene-hydride (p〇lsilyl_hydrides, etc.), aliphatic binder (usually propyl or butyl) and The desired polarity or ionic functional group at the other end. The surface chemistry of the micelle can be easily manipulated by selecting an appropriate covering agent or a combination thereof and the like. Generally, the emulsion is formed by a suitable solvent. Mixing the surfactant above the critical cell concentration, preferably at a concentration greater than 10% by weight 'in some embodiments, from about 15 to about 250 / ❶ (by weight), in some embodiments It is between about 15 and about 20% by weight. Both emulsions and microemulsions can be used in the present invention, and depending on which emulsion is disclosed, microemulsions can be formed from the selected particles and the surfactant. The emulsion is heated and oxygen permeable particles are added. Crosslinkers can be added to form crosslinked micelles in some embodiments. In another embodiment, the oxygen permeable particles are encapsulated into a liposome. A suitable composition can be selected to provide any of the above characteristics. For example, if a desired compatibility with a conventional hydrogel reaction mixture is desired, a phospholipid can be used with other liposomes to form a compound. Suitable liposome forming compounds can include, but are not limited to, DSPC (distearoylphosphatidylcholine) 'HSPC (hydrotated soy phosphatidylcholine) and poly(ethylene glycol) combined with cholesterol, fat and phospholipid, combinations and analogs thereof. 26 201105728 Suitable liposome formation methods include conventional methods such as, but not limited to, mixing the desired components, ultrasonic methods, membrane extrusion, and the like. Examples of the encapsulated solid oxygen permeable particles include X-52-7030 available from Shin Etsu, Inc. (Sakamoto) and 9701 Cosmetic Powder sold by Dow Corning 'This is a bismuth-based polysulfide Formed by dimethicone/vinyl dimethicone cross-linking, and cross-linked polymer coated with Shi Xi, prepared cross-linked poly(dimethyloxane) core and poly ( Poly(silsesquioxane) shells with an average particle size distribution of 800 nm 'range from 0.2 to 2000 nm. The oxygen permeable particles can be incorporated into the hydrogel polymer of the present invention in an amount effective to enhance oxygen permeation. As used herein, "effectively enhances oxygen permeation" means an amount effective to increase the oxygen permeability of the polymer by at least about 10%, at least about 25, compared to the oxygen permeability of a hydrogel polymer having no oxygen permeable particles. %, in some embodiments at least 50%, and in other embodiments greater than 100%. In some embodiments, the compositions of the present invention have an oxygen permeability of at least 25 barrers, at least about 40 barrers, and in some embodiments at least about 6 barrer 'in other embodiments at least about 80 barrers' in other embodiments at least About 100 barrer. The amount of oxygen permeable particles to be added to the reaction mixture can be easily determined by the oxygen permeability of the desired composition and the oxygen permeability of the polymer not containing any oxygen permeable particles. This can be easily achieved by preparing a polymer film having a different oxygen permeable particle concentration, measuring the Dk (oxygen permeability coefficient) of the film, and obtaining an oxygen permeable particle at 100% concentration by extrapolation. . In addition, for the hollow nanostructure, the amount of nanostructure in the reaction mixture 27 201105728 is added, which can be used as described in Journal of Biotechnology 77 (2000) 151-156 "Evaluation of oxygen permeability of gas vesicles from cyanobacterium Anabaena flos-aquae The conventional permeation theory is determined by the oxygen permeability of the system. The oxygen permeability of the encapsulated oxygen permeable particles is determined by the properties of both the oxygen permeable particles and the encapsulating material, including but not limited to particle size, The surface area of the encapsulated particles, the surface composition, the hardness of the encapsulating material and the degree of crosslinking of the shell with the core. For example, in one embodiment, the hydrogel polymer is a mercapto acrylate acid (hydroxyethyl methacrylate, HEMA) with about 2% (weight: g: percentage) methacrylic acid (MAA) (oxygen permeability about 20 barrer) copolymer, PDMS particles (oxygen permeability about 600 barrer) as oxygen permeability The oxygen permeable particles may be added in an amount of at least 15% by weight, and in some embodiments, from 2 Å to about 70% by weight. The amount added may be insufficient to exert an undesirable effect on other characteristics of the resulting composition. For example, when the composition is used to prepare an object that must be clean and useful when used, such as a contact lens, the polymer should not be at the desired thickness. Visible turbidity occurs. In these embodiments, the polymer using the method described below has a haze of less than about 15%, in some embodiments less than about 1 〇0/〇, and in some embodiments less than about 5%. In another embodiment, the object is a contact lens and the 5 osmotic particles are predominantly outside the optical zone. This method allows for the filling of particles, including particles that cause turbidity of the final lens, particle concentration, or both. The efficacy of the present invention is such that oxygen permeable particles can be added to the reaction mixture used to prepare conventional hydrogels. Conventional hydrogels are conventional and comprise homopolymers and copolymers of polyHEMA and polyvinyl alcohol. The comonomers include mercaptoacrylic acid, N-vinyl base σ N-vinylpyrrolidone, Ν-vinylacetamide (Ν_νίηγ1 acetamide), N-ethyl fluorenylamine (N-viny) l methyl acetamide), N,N dimercapto acrylamide, acrylic acid, glyceryl monomethacrylate, MPC (2-mercapto propylene oxyethylphosphocholine), mercapto acrylate, acrylic acid乙乙的( hydroxyethyl acrylate ), Ν-(1, Γ-dioxin-3-oxobutyl) acrylamide, polyethylene glycol monomethacrylate, polyethylene glycol, Combination of polyethylene glycol dimethacrylate, 2-ethoxyethyl methacrylate, 2-methacryloxyethyl phosphorylcholine analog. HEMA homopolymers and copolymers include etafilcon, polymacon, vifilcon, bufllcon, cromllcon, genfilcon, hioxifilcon, lenefilcon, methafilcon, ocufilcon, perfilcon, surfilcon, tetrafilcon. Polyvinyl alcohol homopolymers and copolymers can also be used, including atlafllcon and nelfilcon. It is also possible to use methyl methacrylate with a hydrophilic monomer such as N,N-dimercaptopropenylamine or N-vinylpyrrolidone such as lidofilcon. However, oxygen permeable particles may also be used to increase the oxygen permeability of any hydrogel formulation, including butadiene resin hydrogels such as, but not limited to, balafilcon, lotrafilcon, aquafllcon, senofllcon, galyfilcon, narafilcon, comfilcon, oxyfilcon or siloxyfilcon, and the like. Shi Xi Oxy Resin Water Condensation 29 201105728 Glue. The USAN names listed include all variations of the same name. For example, lotrafilcon includes both lotrafilconA and B. The oxygen permeable particles of the present invention can be directly added to the reaction mixture forming the hydrogel polymer' and can also be absorbed or infiltrated by the hydrogel polymer which is subsequently cured. The reaction components are mixed with oxygen permeable particles to form a reaction mixture. The reaction mixture can optionally include a diluent to aid in the process or to improve compatibility. Suitable diluents are well known in the art and can be determined by the polymer selected. For example, suitable diluents for conventional hydrogels include organic solvents, water, or mixtures thereof. In one embodiment, when a conventional hydrogel is selected as the polymer, organic solvents such as alcohols, diols, triols, polyols, and poly(ethylene) can be used. Polyalkylene glycols. Examples include, but are not limited to, glycerol, glycols such as ethylene glycol or diethylene glycol; boric acid esters of polyols as disclosed in U.S. Patent Nos. 4,680,336, 4,889,664 and 5,039,459; Polyvinylpyrrolidone; ethoxylated alkyl glucoside; ethoxy bis, A; polyethylene glycol; propoxy and ethoxylated alkyl glucoside or acid a mixture of dihydric alcohol; a single phase mixture of a propoxy or ethoxylated alkyl glycoside with a C2_12 dihydric alcohol; ε-caprolactone (ε-caprolactone) and C2_6 Alkanediols or triad adducts; ethoxylated C3-6 alkanols are described in U.S. Patent Nos. 5,457,140; 5,490,059, 5,490,960; 5,498,379; 5,594,043; 5,684,058; 30 201105728 a mixture of 5,736,409,5,910,519. The diluent may also be selected from the group consisting of a defined viscosity and a Hanson cohesion parameter as described in U.S. Patent No. 4,680,336. It may also include one or more crosslinkers, also referred to as crosslinkers' in the reaction mixture, such as ethylene glycol methacrylate ("EGDMA"), trihydrocarbyl propane trimethacrylate ( "TMPTMA"), glycerol trimethacrylate, polyethylene glycol dimethacrylate (wherein the polyethylene glycol has one molecule 1 preferably up to, for example, about 5000), and other polyacrylic acid S and poly(methacrylic acid) g, such as the above-mentioned blocked polyoxyethylene polyol containing two or more decyl acrylate end portions. The crosslinking agent is used in a normal amount, for example, in the reaction mixture, up to 2% by weight of the reaction component. Alternatively, if any monomer component is used as a crosslinking agent, an additional crosslinking agent may be optionally added to the reaction mixture. An example of a hydrophilic monomer which can be used as a crosslinking agent and which does not require the addition of an additional crosslinking agent to the reaction mixture in use includes a polyol polyoxyethylene containing two or more terminal methyl acrylate moieties. The reaction mixture may contain additional ingredients such as, but not limited to, TJV absorbent materials, medical agents, antibacterial compounds, reactive dyes, colorants, copolymerizable or non-polymerizable dyes, release agents, or combinations thereof. A polymerization initiator may also be included in the reactant. The polymerization initiator includes lauryl peroxide, benzoyl peroxide, isopropyl carbonate (iS0pr0pyi percarb〇nate) or azo which generates radicals at a moderately high temperature. a compound such as azobisisobutyronitrile, or 31 201105728 photoinitiator system such as aromatic alpha-hydroxy ketones, alkoxyoxybenzone, acetophenone, Systems such as acylphosphine oxides, bisacylphosphine oxides and mono-diketone tertiary amines or mixtures thereof. Examples of photoinitiators are 1-hydroxyphenyl ketone, 2-hydroxy-2-indolyl-1-phenylacetone-1-1, bis(2,6-dioxabenzophenyl)-2,4 -4-tridecylpentylphosphine oxide (DMBAPO), bis(2,4,6-trioxalylphthalenyl)-phenylphosphine oxide (Irgacure 819), 2,4,6-triphenylbenzene Biphenylphosphine oxide, 2,4,6-trioxabenzoquinonebiphenylphosphine oxide, benzoin methyl ester, and camphorquinone and ethyl 4-(N,N A combination of -diammonium benzoate commercially available visible light starting systems including Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 819, Irgacure 1850 (both available from Ciba Specialty Chemicals) and Lucirin TPO starter (available From BASF). Commercially available UV light starters include Darocur 1173 and Darocur 2959 (Ciba Specialty Chemicals). These and other possible starters are used in Volume III, Photoinitiators for Free Radical Cationic & Anionic Photopolymerization, 2nd Edition by JV Crivello K. Dietliker; edited by G. Bradley; John Wiley and Sons; New York; 1998 It is disclosed and incorporated herein by reference. An effective amount of an initiator is used in the reaction mixture to initiate photopolymerization of the reaction mixture, for example, from about 0.1 to about 2 (by weight) per 100 parts of the reaction monomer. The polymerization of the reaction mixture can be initiated by heating, visible light, ultraviolet light or other means depending on the use of the polymerization initiator 32 201105728. Alternatively, the initial action can be carried out without a photoinitiator, such as an electron beam. However, in an embodiment, when a photoinitiator is used, preferably the initiator comprises bis-decylphosphine oxide (1^&〇71卩11〇5卩出 116(^(^), for example, double (2,4,6-trimethoxybenzoate)-phenylphosphine oxide (Irgacure 819®) or a 1-hydroxycyclohexyl phenyl ketone with bis(2,6-dioxabenzoguanidinyl)_2 a combination of 4_4_trimethylpentylphosphine oxide (DMBAPO), and a preferred initial polymerization method is to utilize visible light. A preferred embodiment is bis(2,4,6-trioxanoxy). Phenylphosphine oxide (Irgacure 819®). For example, biomedical devices or objects in some ophthalmic device embodiments can be mixed with a polymerization initiator by mixing the reaction components with the diluent (if used). Hardening under appropriate conditions to prepare a product which can be formed into a suitable shape by forming slats or cutting and the like. Alternatively, the reaction mixture can be placed in a model having the desired shape and then cured into The desired object. For example 'When the reaction mixture is used to form a contact lens, any known in contact lens system Processes for the production of a solidified reaction mixture, including both spin casting and static casting, may be used. U.S. Patent Nos. 3,408,429 and 3,660,545, the disclosure of which are incorporated herein by reference. A static casting process. In an embodiment, the method of making a contact lens comprises by directly molding a reaction mixture to produce a polymer of the invention 'which is economical and capable of precisely controlling the final shape of the hydrated lens. For this method, the reaction mixture It is placed in a mold having the shape of the final desired lens, and the 'reaction mixture is controlled by the reaction conditions to polymerize the reaction components to produce a polymer/diluent mixture having the final desired lens shape. 33 201105728 Composition of the Invention The balanced nature of the material makes it particularly useful. In one embodiment, the composition is used to make lenses, particularly contact lenses, which include clarity, water content, oxygen permeability and junction angle. In one embodiment, the biomedical device is a contact lens having a water content greater than about 20%. In some embodiments, greater than about 30%. Clarity herein means that there is little visible turbidity. A clean lens has a haze value of less than about 15 Å/0 compared to a CSI lens, preferably. Less than about 100°/〇. Using a conventional hydrogel as a polymer has the added benefit of producing an object such as a contact lens' comprising a junction angle of less than about 100 and a modulus of less than about 100 psi. The contact lens formed from the composition of the present invention has an average junction angle (advance) of less than about 80°, less than about 75, and in some embodiments less than about 70. In some embodiments, the invention The object has the above oxygen permeability, water content and junction angle combination. All combinations of the above ranges are considered to be within the scope of the invention. Haze measurement The clarity here means that there is almost no visible turbidity. The sharpness can be measured by % haze, which is calculated from the transmission value. Transmission can be measured by ASTM D1003 using an integrating sphere oximeter. Performing this measurement is to obtain 4 different continuous readings, and measure the photocell output Τ! = the sample and the optical trap at the exit position, the reflectance standard at the position is 2 = the sample at the position and the reflectance standard, Leaving the position of the light trap D - 3 in the position of the light trap, leaving the position of the sample and reflectance standard 34 201105728 Τ '4 = the reflectance of the sample at the position and the light brown 'away position'; _ per reading The number represents the incident light, the sample transmission ~ light, the light scattering caused by the instrument, the light scattering caused by the instrument and the sample, the total transmittance (Tt and the diffuse transmittance into the transmittance) Td is calculated as follows ^t= T2/Tl

Td= [T4 _ Kivm/T! The haze percentage is calculated as follows. Haze percentage = Td/Ttxl00 Water content The water content contact lens is calculated as follows: Three sets of three lenses are placed in the filling solution for 24 hours. Apply each lens with a damp cloth and plant the weight. The lens was dried for 4 hours under a 6 〇 C pressure of G. 4 inch column to dry the lens. The water content calculation method is as follows: % water content = U weight ~ dry weight) xl00 wet weight

Calculate and report the average value of the sample moisture and the standard L 201105728 Calculate the modulus with a fixed crosshead using a kinematic tensile tester equipped with a load cell that is lowered to the initial measured height. Suitable measuring machines include the Instron model 1122. A dog bone sample taken from a _1.00 lens having a 0.522 inch length, a 0.276 inch "ear" width and a 0.213 inch "neck" width was placed in the clip and elongated at a constant rate of 2 in/min until it broke. The initial measurement length (Lo) of the sample and the length (Lf) of the sample when it is broken are measured. Twelve samples of each composition were measured and the average value was reported. The percentage of elongation is =[(Lf _ Lo)/Lo] χ 100. The tensile modulus is measured linearly at the beginning of the stress/strain curve. Advancing Contact Angle The advancing contact angle was measured using a lens with a -1.00 diopter as follows. A strip of approximately 5 mm width was cut at the center of the lens and equilibrated in the filling solution to prepare 4 samples per set. When the sample was immersed or removed from the buffer, the wetting force between the lens surface and the borate buffer was measured using a Wilhelmy microbalance at 23 °C. Use the following equation F = 2 gpcosq or q = cos-1(F/2 gp) where F is the wetting force, g is the surface tension of the probe liquid, p is the circumference of the sample meniscus, and q is the contact angle. The advancing contact angle is derived from the experimental portion of the wetting when the sample is immersed in the filling solution. Each sample was cycled 4 times and the results were averaged to obtain the contact angle of the lens. 36 201105728 Oxygen permeability (Dk, oxygen permeability coefficient)

The Dk (oxygen permeability coefficient) is calculated as follows. The lens was placed in a polarographic oxygen sensor consisting of a 4 mm diameter gold cathode and a silver ring anode, followed by a support mesh cover at the upper end. The lens was exposed to an atmosphere containing 2.1% humidified oxygen (〇2). The sensor is used to measure the oxygen diffusing through the lens. One lens is stacked on top of the other to increase the thickness or to use a thicker lens. The L/Dk' of 4 samples with significantly different thickness values was measured and plotted against the thickness. The reciprocal of the regression slope is the Dk (oxygen permeability coefficient) of the sample. Commercially available contact lenses were measured using this method as a reference value. The Balafilcon A lens (-1.00) purchased from Bausch & Lomb was measured to be approximately 79 barrer. Etafilcon lenses are 20 to 25 barrer. (1 barrer = ΙΟ·1. (cm3 of gas X cm2) / (cm3 of polymer x sec x cm Hg)). The content of strontium activated by neutrons was activated by neutrons to measure the strontium content. All samples, standards and quality control products were irradiated for 15 seconds to decay for 120 seconds and count for 300 seconds.

The 1779 keV gamma ray of the 28A1 ( tl/2 = 2.24 minutes) decay is measured to determine the erbium concentration. 28A1 is produced by a (n, P) reaction of 28Si. Three geometrically equivalent 矽 standards were analyzed in this sample batch. The standard strain was prepared by adding Shishi to the pulp, and Shi Xi was from 1 〇 ±〇.〇511^/11^ certified solution standard (high purity standard). The result of the 28A1 signal from the vial of the sample was irradiated from the white high-density polyethylene, and the result was blank corrected. NIST SRM 1066a Octaphenylcyclotetrasiloxane was analyzed along with the sample as a quality control check for this analysis. The recognition in SRM 37 201105728 is about 14.14 ± 0.07% Si (% by weight). The average of three 10 mg SRM aliquots was analyzed to be 14.63 ± 0.70% Si (% by weight). Surface Thickness The surface roughness was measured by atomic force microscopy (AFM) using a Nano Instruments Nanoscope at a scan size of 20 μm and a scan speed of 7.181 Hz. Each sample was scanned 256 times using a data size of 1000 μηη. The positions of X and Y used are -19783.4 and a 42151.3 μπι, respectively. Scanning Electron Microscopy oi Lenses MM Surface #尨.· Captures surface images in three positions (left, right, and center) from the concave and convex surfaces of all samples. Using the FEI Quants Environments SEM, the 25 kV accelerating voltage (Cigaplus voltage) and the 5 nA scanning beam current were used to image at 5,000 magnifications at 8 £ and BSE imaging. / /册#/续# ·. Use the same sweeping beam conditions as the surface image to capture the contour (wearing the face). The overall section of the H-fiber film cannot be named as 5 thousand times. The overall cross section. From the concave surface of the lens at 5 thousand magnifications (above = 3 steps: way to capture the image, in the - picture-to-face manner through tl: the final image phase. Then use 201105728 to describe but not limit the invention. It is merely intended to represent a method of practicing the invention. In the field of contact lenses, the knowledgeable and other experts may implement the invention by other methods. However, those methods are still considered to be within the scope of the invention. The material is defined as follows: BAGE · · Boric acid glycerol ester DBS : ^-Dodecylbenzenesulfonic acid purchased from Sigma Aldrich HEMA : 2-hydroxyethyl methacrylate (99% Purity) MAA : Methacrylic acid (99% purity) OHmPDMS : Mono-(3-methylpropenyloxy-2-hydroxypropoxy)propyl terminated, mono-butyl terminated polydidecyloxyne ( 612 Molecular Weight), DSM Polymer Technology Group SiMAA DM : Methyl-bis(trimethyldecyloxy)-decane-propyl glycerol dimethacrylate vinegar DSM Polymer Technology Group, according to US US2005/0255 Prepared in the preparation examples of 231. Si microparticles: crosslinked poly(dimercaptononane) core and poly(sesquioxane) shell (Shin Etsu, Inc.) 5252-7030 In the range of 0.2-2000 nm 'the average size distribution is 800 nm, as determined by the manufacturer by SEM.) Examples 1-11 In the BAGE dilution, the monomer mixture contained 94.90 % HEMA ' 1.94 % MAA ' 0.95 %Norbloc ' 1.33 % Irgacure 1700, 0.77 % EGDMA, 0.09 % TMPTMA and 0.02 % Blue HEMA (w/w) (52:48 monomer · dilution), known as Reactive Monomer Mixture (RMM) Prepared and used in the examples. In the preparation of Examples 1-10, the mass of the desired mash was added to the amber scintillation vial, followed by the addition of etafilcon RMM (10 g). vac (10) in a vacuum (i 〇 minutes) Prior to this, the scintillation vial was capped and rolled for 2 hours to prepare a lens. 39 201105728 For each formulation, each early agent is mixed into an individual front arc by a pipette to prepare a lens. In the first example, in the absence of BAGE, half of the desired microparticles were suspended in 2.4 g of ethylene glycol, and the other was prepared in a 5.2-g monomer mixture. Further, the mixture was diluted with bage and homogenized by mechanical stirring with shear. The resulting monomers were degassed for 10 minutes in a vacuum (h vacwo). The high viscosity of Example 11 requires the provision of a front arc via a pressurized syringe. A diopter-1.0 lens was prepared using a Zeonor (Zeon Chemical) front/rear arc. It was hardened in a nitrogen (N2-) rinse glove box at 5 ° C for 10 minutes using a TL03 lamp (400 nm) at a brightness of 3·4 mW/cm 2 . The lenses were demolded and released to a deionized water bath at 90 ° C prior to storage in individual crimped sealed glass vials containing borate buffer. All lenses were sterilized in a pressure cooker at 121 ° C for 30 minutes before analysis. Table 1 Experimental No. SiMP Amount (g) Amount of diluent (g) Reactive monomer (g) %Si in the lens MP.heo %SlTheo in the lens 1 0.000 4.8 5.2 0.0 0.0 2 0.125 4.8 5.2 2.4 0.9 3 0.250 4.8 5.2 4.6 1.7 4 0.500 4.8 5.2 8.8 3.3 5 0.750 4.8 5.2 12.6 4.8 6 1.000 4.8 5.2 16.1 6.1 7 1.250 4.8 5.2 19.4 7.4 8 1.500 4.8 5.2 22.4 8.5 9 1.750 4.8 5.2 25.2 9.6 10 2.800 4.8 5.2 35.0 13.3 11 15.600 0.0 5.2 75.0 28.5 40 201105728 Measure the Dk (oxygen permeability coefficient), water content and Si content of each pair of lenses. The results for each of the mixtures are listed in Table 2 below. From the data, it can be seen that when the particles are increased from 0% to 64.3%, the obtained Dk (oxygen permeability coefficient) is increased to 76 units. Figure 1 is a graph of Dk (oxygen permeability coefficient) versus ruthenium particle concentration for the final lens. Figure 1 shows a positive and nonlinear polynomial trend. When a graph of the amount of elemental Si in the lens is plotted as Dk (oxygen permeability coefficient) (as shown in Figure 2), a similar nonlinear polynomial is obtained. For comparison purposes, two separate data points are inserted in Figure 2 to represent the current SiH reference, Oasys (%Si = 15.0, Dk = 104) and Advance (%Si = 13.0 ' Dk = 60). By comparing the data obtained in Example M1 with the reference, the addition of ruthenium particles does increase the Dk (oxygen permeability) of the final polymer. Table 2 Experimental No. Lens of the lens Si NP Lens %SiThen %Si〇bS of the lens % Water content Dk (oxygen permeability coefficient) Unit 1 0.0 0.0 0 60.5 20 A _ 2 2.35 0.9 1 60.0 20 3 ------ 4.59 1.7 1.7 h ----- 2 58.7 ND 4 8.77 3.3 3 58.5 22 5 12.61 4.8 5 58.2 23 6 16.13 '~6Λ ~~~~~ 6 57.6 23 7 ---- 19.38 1 7.4 7 57.5 25 8 -- ---- 22.39 8.5 9 58.5 29 9 25.18 9.6~ 9 56.9 31 10 35.00 a 13.3 -------- 13 57.3 34 11 64.3 28.5 —------- 24 55.7 76 201105728 Figure 3 shows the implementation A scanning electron microscope (Sem) photomicrograph of 〇. All of the positions formed by the scanning electron microscope showed a very coarse surface containing many particles. Generally, the morphology of the sample (on both sides of the lens) is uniform with the particle clusters. Individual particle sizes cannot be measured due to particle formation clusters. By observing the scanning electron microscope image, it is estimated that the particle size is between about 6 〇〇 and about 1000 nm. The cross-section of the scanning electron microscope of the lens appears to be almost homogenous to the surface image. The surface image includes a rough seam morphology caused by clusters of particles. Example 12-15: Preparation of Sil 〇 xane Nano-Particles from Free Radical Micro-Emulsion Polymerization of OHmPDMS and SiMAA DM was used as if it were received Available from Wako Specialty

Water Company's water-soluble starter VA-044. Each of the particle dispersions having the compositions listed in Table 3 was prepared as follows. Water and DBS were added to a 3-neck jacketed reaction flask equipped with a mechanical stirrer and a hot probe. The water and DBS were heated to 44 ° C and stirred under a nitrogen sealer (Nitrogen Blanket) until a clear microemulsion was formed. After stirring for 30 minutes under a nitrogen seal at 300 rpm, a solution of VA-044 (200 mg in 1 mL DI water) was added by syringe. Both OHmPDMS and SiMAADM were mixed together and the resulting mixture was added dropwise to the microemulsion while stirring at 300 rpm. After all the mash mixtures had been added (about 3-4 hours), the addition funnel was removed and the flask was sealed with a vented rubber septum. The reaction was maintained overnight at 44 ° C under nitrogen. On the morning of 201105728, add an additional 200 mg of VA-044 in 1 mL of deionized water to the microemulsion. The microemulsion was allowed to react for another 4 hours. The characteristics of each dispersion listed in Table 3 were measured by Dynamic Light Scattering (DLS) of a Malvern-ZetaSizer Nano-S meter. After each reaction was completed, one sample was removed and diluted 10 times. The diluted dispersion was analyzed by DLS to obtain a Z-average particle size distribution. The measures were also measured after each disseminated dialysis. The data from the DLS is processed using the CUMULANTS analysis function included in the meter software. All generated data are quite consistent with the CUMULANTS curve. The corresponding PDI width and %?〇1 of each resulting Silicone ME and its hydrodynamic upper diameter are listed in Table 4 below. Table 3 Experimental No. OHmPDMS (g) SiMAA DM (g) H20 (g) dbs^ (g) VA-044 (mg) 12 24 96 350 80~~ 400 13 48 72 350 80 400 400 14 72 48 350 80 15 96 Wide 24 350 80 400 Experiment No. 7 Λ ^ r /v / . . PDI Width (nm) %PDI 12 46 7 rTPrT^--uH ynm; 16.2 34.7 13 34 8 ΠΊ 〇, ------— 10.3 29.6 14 44 9 (C\ ---— 15.7 35.5 15 65.1 (0.2) ~~-- 35.5 54.6 " °Xuandaozheng can be kept stable in water for at least two months. Slight agitation can make any sinking object easy The ground is re-dispersed. 43 201105728 A dispersion of 50:50 HO-mPDMS and SiMAA DM in water was prepared by the above method. The dispersion was deionized with a 3500 MWCO regenerated cellulose dialysis membrane of Spectrap®. The resulting dispersion can be stable in water for more than two months. The frequency histograms for Examples 12-15 are attached here. The data from Example 12-15 is highly correlated with the use of CUMULANTS fit, which shows particle size The Gaussian distribution 'and indicates that the aggregation in the dispersion is small or absent. This result is shown in the histograms of Figures 4 to 7. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a plot of Dk (oxygen permeability coefficient) versus concentration of ruthenium particles in a polymer. Figure 2 is a plot of Dk (oxygen permeability coefficient) versus strontium content concentration. Figure 3 is a graph containing 800 nm Shin SEM micrograph of Etsu POSS/PDMS microparticles based on etafilcon. Figure 4 is a histogram of particle size volume distribution of SiME-OHmPDMS 20. Figure 5 is a histogram of particle size volume distribution of SiME-OHmPDMS 40. The particle size volume distribution histogram of SiME-OHmPDMS 60. Figure 7 is a histogram of the particle size volume distribution of SiME_OHmPDMS 80.

Claims (1)

201105728 VII. Patent Application Range: 1. A composition comprising a hydrogel polymer having an oxygen-enriching particle having an oxygen-enhancing effective amount, the oxygen-permeable particle having an oxygen permeability of at least about 100 barrer and The average particle size is less than about 5 〇〇〇 mn 〇 2. The composition of claim 1, wherein the composition has an oxygen permeability of at least about 40 barrer. 3. The composition of claim 1 wherein the composition has an oxygen permeability of at least about 60 barrer. 4. The composition of claim 1, wherein the composition has an oxygen permeability of at least about 100 barrer. 5. The composition according to claim 1, wherein the oxygen permeable particles are non-reactive. 6. The composition of claim 1, wherein the oxygen permeable particles have an oxygen permeability of from about 100 barrers to about 6000 barrers. 7. The composition of claim 1, wherein the oxygen permeable particles have an oxygen permeability of from about 300 barrers to about 1000 barrers. 8. The composition of claim 1, wherein the oxygen permeable particles have an average particle size of less than about 800 nm. The composition of claim 1, wherein the oxygen permeable particles have an average particle size of less than about 600 nm. 10. The composition of claim 1, wherein the oxygen permeable particles have an average particle size of less than about 200 nm. 11. The composition of claim 1, wherein the oxygen permeable particles are encapsulated. 12. The composition of claim 11, wherein the oxygen permeable material is encapsulated with a coating selected from the group consisting of a coating, a microcell, a liposome, or a combination thereof. 13. The composition of claim 12, wherein the oxygen permeable material is encapsulated with a coating composition comprising a hydroxyl group. 14. The composition of claim 12, wherein the oxygen permeable material is encapsulated with a coating composition selected from the group consisting of crosslinked or non-crosslinked core/shell type micelles. 15. The composition of claim 1, wherein the oxygen permeable particles have an average particle size of less than about 100 nm. 16. The composition of claim 12, wherein the encapsulating material is compatible with the hydrogel polymer. 46 201105728 17. According to the composition of the application, the composition of the article has a haze of less than 100%, and the refractive index between the layers is 10%. (10) Refractive index. Peak U refraction 1M 艮 According to the full-time (4) component of the item i is less than Qing. The haze and the oxygen permeable barium have a refractive index of between about 1.45. There is a composition of the eighth item in the force 1.37, wherein the hydrogel polymerization is selected from the group consisting of the ridges HEMA and the PVQH (4) (4) group. *~ 〇· According to the 13th item of the patent scope a composition, wherein the hydrogel polymer further comprises a polymer selected from the group consisting of: acid, methacrylic acid, ethylene, etc.: sold: N-vinyl methyl acetamide, N, N-didecyl acrylamide, acrylic acid, glycerol mono Acrylate, MPC (Ishiham monomer), decyl methacrylate, hydroxyethyl acrylate, N_(U'_dimethyl-3-oxobutyl) propylene amine, polyethylene glycol monodecyl acrylate a group consisting of polyethylene glycol dimercapto acrylate, 2-ethoxyethyl methacrylate, oxyethylphosphonium 2-mercapto acrylate, and a mixture thereof. The composition of item 1 wherein the oxygen permeable material is selected from the group consisting of crosslinked polydioxanoxane, poly((tridecyldecyl)propyl (such as 2,2-bis(trifluoromethyl)) a group consisting of a copolymer of _4,5-difluoro-1,3-dioxazole with tetrafluoroethylene, a fluorinated PDMS polymer, and mixtures thereof. 47 201105728 22. Scope of application The composition of item i, wherein the oxygen permeable material is selected from the group consisting of a crosslinked fluoropolymer, a crosslinked polydialkyl siloxane polymer, a self-assembled decane, a rigid siloxane material, and combinations thereof. 23. The composition according to claim 5, wherein the encapsulating material is selected from the group consisting of a liposome, a microcell or a polymer structure. The composition of the 23rd item, wherein the package The sealing material comprises a polymer structure selected from the group consisting of a cation, a cation, a zwitterion, and a mixture thereof. The lining, and the composition 25. The material according to the item i of the patent scope has less than about Average particle size at 1000 nm. Oxygen particles 2 6. According to the scope of the patent application! The composition of the material particles contains - loosely crosslinked poly ((4) $ encapsulated oxygen-permeable shell. Core and - pro 27. The composition according to claim 12, which is biocompatible. The encapsulating material is a composition comprising a hydrogel polymer having a sub-size of less than about 5000 nm and a sufficient amount.曰有平句4 has an oxygen permeability of at least about 10 barre The oxygen permeable particle of the r is a composition of the first aspect of the invention, wherein the oxygen permeable particle has an average particle size of less than about 1 〇〇 nm. The composition of claim 1 further comprising a haze of less than about 15%. 31. The composition according to claim 1, wherein the oxygen permeable particle is spherical. 32. The composition of the item, wherein the oxygen permeable particle comprises a hollow nanostructure having an oxygen permeability of at least about 200 barrer and an average particle size of less than about 500 nm at its longest dimension. 33. The composition of claim 32, wherein the composition has an oxygen permeability of at least about 25 barrer. 34. The composition of claim 32, wherein the hollow nanostructure is spherical and has an average particle size of less than about 400 nm. 35. The composition of claim 32, wherein the hollow nanostructure is spherical and has an average particle size of from about 1 Torr to about 1 〇〇 nm. 36. The composition of claim 32, wherein the hollow nanostructure is elongated and has an average diameter of from about 2 Torr to about 丨〇 m n m and an average length from H (8) to about 5000 nm. 49. The method of claim 32, wherein the hollow nanostructure comprises a critical pressure of at least 0.05 MPa. 38. The composition of claim 32, wherein the hollow nanostructure comprises a critical pressure of at least 0.2 MPa. 39. The composition of claim 32, wherein the hollow nanostructure comprises a casing surrounding an inflated space, and wherein the interface of the outer casing and the inflated space comprises at least one water impermeable material. 40. The composition of claim 39, wherein the outer shell further comprises at least one hydrophilic material encapsulating the at least one water impermeable material. 41. The composition of claim 32, wherein the hollow nanostructure is a balloon protein. 42. The composition of claim 41, wherein the balloon protein is encapsulated in a polymer or copolymer comprising a repeating unit of 2-hydroxyethylmercaptopropenyl. 43. The composition of claim 32, wherein the hollow nanostructure is encapsulated in a polymer or copolymer comprising repeating units derived from 2-hydroxyethylmercaptopropenyl. 44. The composition of claim 41, wherein the balloon protein comprises a cross-linked wall. 50. The composition of claim 32, wherein the hollow nanostructure is formed from at least one synthetic material. 46. The composition of claim 32, wherein the hollow nanostructure is formed by emulsion polymerization via a template, and the template is removed via dissolution after the nanostructure is formed. 47. The composition of claim 32, wherein the hollow nanostructure comprises an outer shell and at least a portion of the outer shell comprises at least one selected from the group consisting of metal oxides, nitride sheds, transition metal sulfides, metals An inorganic component of a group consisting of graphite flakes, ilmenite oxides, and combinations thereof. 48. The composition of claim 32, wherein the hollow nanostructure is constructed as a cylinder having a tapered cap end. 49. The composition of claim 32, wherein the hollow nanostructure has a composition selected from the group consisting of regular or irregular polyhedrons, ellipsoids, cones, spheroids, and combinations thereof. The shape of the group. 50. The composition of claim 32, wherein the hollow nanostructure is reactive. 51. The composition of claim 32, wherein the synthetic hollow nanostructure is crosslinked. 201105728 52. A medical device formed from the composition of item 1 of the scope of the patent application. 53. An ophthalmic device formed from the composition of item 1 of the scope of the patent application. 54. A contact lens formed from the composition of item 1 of the scope of the patent application. 55. A contact lens comprising a hydrogel polymer having an oxygen-enhancing effective amount of oxygen permeable particles distributed over a region outside the optical zone of the contact lens, the oxygen permeable particles having a flow of at least about 1 barrer Oxygen permeability and average particle size between about 200 nm and 100 microns. 52